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Applied Energy 95 (2012) 3137

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Carbon based nanotubes and nanopowder as impregnated electrode structures


for enhanced power generation: Evaluation with real eld wastewater
G. Mohanakrishna a, S. Krishna Mohan b, S. Venkata Mohan a,
a
b

Bioengineering and Environmental Centre (BEEC), CSIR-Indian Institute of Chemical Technology, Hyderabad 500 607, India
Defence Research and Development Laboratory (DRDL), Kanchan Bagh, Hyderabad 500 058, India

a r t i c l e

i n f o

Article history:
Received 9 December 2011
Received in revised form 17 January 2012
Accepted 24 January 2012
Available online 14 March 2012
Keywords:
Multi walled carbon nanotube (MWCNT)
Carbon nanopowder (CNP)
Microbial fuel cell
Electrogenic activity
Wastewater treatment
Distillery wastewater

a b s t r a c t
Carbon based multiwalled nanotubes (MWCNT) and nanopowder (CNP) impregnated using conductive
epoxy resin on anodic surface were evaluated for bioelectricity generation in single chambered microbial
fuel cells in comparison with plain graphite anode (MFCP). The study demonstrated the positive function
of carbon nano structures impregnated anode with respect to power generation. MFCMWCNT exhibited
higher electrogenic activity (267.77 mW/m2) followed by MFCCNP (168.45 mW/m2) and MFCP
(107.51 mW/m2). MFCMWCNT and MFCCNP showed 148% and 57% enhancement in the power generation
respectively compared to MFCP. Microbial mediators were also found to be more effective with modied
anodes operation. Impregnation with nano material facilitates higher surface area that enables higher
charge transfer from anolyte to electrodes. Impregnated anodes showed marginal inuence on substrate
degradation. Further, feasibility of MWCNT impregnated anode was evaluated with real eld distillery
wastewater which depicted good electrogenic activity (245.34 mW/m2) and yield (3.43 W/m3).
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Microbial fuel cells (MFC) are the devices that facilitate the production of electrical energy from organic wastes using exoelectrogenic bacteria as biocatalyst [14]. Anodic oxidation and cathodic
reduction reactions are the key controlling factors for electrogenic
activity in MFC. The microorganisms oxidize the organic matter
leading to release of electrons and protons. These protons will
transfer to the cathode through membrane generating the potential difference between anode and cathode resulting in an electron
ow (current) through the external circuit. Anode plays a crucial
role in MFC operation which is hub for various bio-electrochemical
reactions and helps to mediate electron transfer to the electrode
from exoelectrogens [35].
High electrical conductivity, chemical stability, inert nature
(non-oxidative), non self-destructive and catalytic activity, sustainability of its properties with time and high surface area are
some of the important properties of the anode which can inuence
the performance of MFC. However, the susceptibility of anode to
microbial growth, afnitive mechanical contact and synergistic
interaction of the biocatalyst with anode (biocompatibility) are
also important to mediate the electron transfer [5,6]. Based on
the economics, practical applicability and efcient performance

Corresponding author. Tel.: +91 40 27191664.


E-mail address: vmohan_s@yahoo.com (S. Venkata Mohan).
0306-2619/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2012.01.058

carbon based electrodes are being used by many researchers


worldwide. Many forms of carbon based materials with modications were studied viz., carbon cloth [7], carbon felt [8], carbon
foam [9], reticulated vitreous carbon (RVC) [10], graphite sheets
[5,1113], graphite rods [14], graphite granules [15] and graphite
ber brushes [8,16] as anodic materials. The performance of these
materials again depends on many factors, including electrode spacing, anolyte conductivity and substrate nature [7,17,18].
The application of MFC for wastewater treatment and bioenergy
production requires the use of high efcient electrode materials
that are electrochemically and biologically stable, along with high
specic surface area and electrical conductivity [19,20]. Nanotechnology is a rich multidisciplinary eld having inputs from many
disciplines of sciences with versatile advantages for wide varieties
of applications [21]. Nanostructures with large surface area facilitate higher reaction kinetics and thus improve power density of
fuel cells [2225]. Multiwalled carbon nanotubes (MWCNT) used
for the preparation of modied anode was evaluated for the
improvement of MFC performance using Enterobacter cloacae as
biocatalyst [26]. Bionanocomposites of Staphylococcus aureus/carbon nanotubes were evaluated for their biocompatibility with different types of carbon nanotubes (CNT) [26,27]. Carbon nanotubes
and nanopowder are the possible anodic coating materials used in
MFC which are having more open structures than other forms of
carbon based electrodes. Macroscale porous CNT-textile electrodes
with 3D structure were found to afford an open structure for biolm growth, enabling internal colonization of microora [2830].

32

G. Mohanakrishna et al. / Applied Energy 95 (2012) 3137

In this communication, MWCNT and carbon nanopowder (CNP)


were impregnated on the surface of anode to study their role in
improving the performance of fuel cell by using wastewater as substrate. Carbon nano-structures with higher surface area help to improve apparent surface area of the anode which will have positive
inuence on the fuel cell performance. Carbon nanotubes exhibit
excellent electron transfer characteristics with a high surface area
to volume ratio and also provides a viable support for biolm
growth [31]. Impregnation or immobilization of nano-structures
will have good compatibility in conductivity/charge transfer. Bioelectrochemical analysis was performed to understand the performance of fuel cells with different anodes. The practical application
of the results obtained with the above objective was also evaluated
using real eld distillery wastewater (DW) as substrate under similar operating conditions. Based on the results obtained in this
study, it can be assumed that the application of nanotechnology
can be extended to bio-electrochemistry for the development of
advanced MFC technology.
2. Experimental section
2.1. Preparation of anodes
Three types of anodes with variable surface coatings/impregnation viz., multiwalled carbon nanotubes (MWCNT, SigmaAldrich
636835), carbon nanopowder (CNP, SigmaAldrich 633100) and
plain/virgin graphite (without any surface coating) were evaluated
in three different fuel cells. MWCNT (95% pure) has a surface area
of 40300 m2/g with a diameter of 110170 nm and length of 5
9 lm. CNP (99% pure) has a surface area of >100 m2/g with particle
size of <50 nm (BET). These specications were given by the manufacturer. Two component of epoxy conductive adhesive blended
in 1:1 ratio was applied as smear on electrodes (non-catalyzed
graphite plates; 5  5  1 cm (l  b  h); surface area 70 cm2).
Subsequently, carbon nanotubes and carbon nanopowder were
uniformly sprayed separately on the smeared electrodes. After
impregnation, the electrodes were allowed for air drying for 6 h
at room temperature (28 2 C). The amount of nano structures
consumed to coat on 70 cm2 electrodes was varied for both
MWCNT (275.6 mg) and CNP (741.5 mg). Prior to use, the electrodes were soaked in deionized water for a period of 24 h at pH 7.
2.2. MFC conguration
Fuel cells were fabricated in the laboratory using perspex
material using NAFION 117 (SigmaAldrich) as proton exchange
membrane (PEM) with a total/working volume of 0.50/0.45 l. The
modied/impregnated electrodes along with non-catalyzed graphite were used as anodes. Non-catalyzed graphite plates
(5  5  1 cm (l  b  h); surface area 70 cm2) was used as
cathode. PEM was sandwiched between anode and cathode after
pre-treatment [32,33]. Anode was submerged in the wastewater
and top portion of the cathode was exposed to air while bottom
portion was xed to PEM and exposed to wastewater. Copper wires
were used for contact with electrodes after sealing with. In the design provisions were made for sampling ports, wire input points,
inlet and outlet ports. All the three open-air cathode fuel cells with
suspended growth were operated in fed-batch (up-ow) mode.
2.3. Operation
Anaerobic consortia collected from large scale UASB reactor
treating composite wastewater was used as biocatalyst in the anode chamber of all three MFC. Prior to startup of the operation,
anodic chambers of all three MFC were inoculated with mixed

microora (3.6 g VSS/l) through feed (0.5 l). Fuel cells were operated in the fed-batch (up-ow) mode at neutral pH (7.0 0.15) under anaerobic microenvironment. After inoculating, designed
synthetic wastewater [DSW, composition in g/l (glucose-3.0,
NH4Cl-0.5, KH2PO4-0.25, K2HPO4-0.25, MgCl2.6H2O-0.3, FeCl30.025, NiSO4-0.016, CoCl2-0.025, ZnCl2-0.0115, CuCl2-0.0105,
CaCl2-0.005 and MnCl2-0.015)] was fed for ve cycles at an organic
loading (OL) of 3.65 kg COD/m3 to adopt the culture to system
microenvironment. Anolyte was re-circulated at 100 ml/h using
peristaltic pump in order to reduce the substrate gradient. Before
changing the feed, inoculum was allowed to settle down for
30 min and then exhausted feed (0.4 l) was replaced with fresh
feed. The settled inoculum of 0.1 l was used for subsequent operations. Feeding, decanting, and recirculation operations were carried
with peristaltic pumps. The anode chamber was sparged with oxygen free N2 gas for 4 min after every feeding and sampling event to
maintain anaerobic microenvironment. Similarly, MFCDW was
operated with real eld distillery wastewater (COD-82.20 g/l,
TDS-21.60 g/l, VFA-1.94 g/l, SS-1.10 g/l, pH-4.21, color-120,000 Hazen units, total alkalinity-4.00 g/l, chlorides-4.10 g/l, sulfates0.10 g/l) to evaluate the practical application of the above study
under similar operating conditions. MWCNT impregnated electrode was used as the anode in this case. On 24 h of regular intervals, the samples were collected from anode chamber and
preserved at 4 C.
2.4. Bio-electrochemical analysis
Current output parameters and substrate degradation were
considered as the two key parameters to evaluate the performance
of fuel cells. Potential difference/open circuit voltage (OCV) and
current (I; measured in series at 50 X) were recorded on digital
multi-meter. Power (mW) was derived from P = IV equation. Power
density (mW/m2) and current density (mA/m2) were calculated
with the function of surface area of anode (m2). Power yield (W/
kg CODR) was obtained by relating power with the amount of
COD removed. Volumetric power production (mW/m3) was calculated based on maximum power generated in a cycle in relation to
total liquid volume of the anode. Bio-electrochemical behavior of
MFC in association to mixed consortia was studied in situ employing cyclic voltammetry (CV) using potentiostat-glavanostat system
(Autolab, PGSTAT12, Ecochemie). CV was recorded by applying a
potential ramp at a scan rate of 30 mV/s over the range from
+0.5 to 0.5 V to working electrode (anode of MFC) to gradually
change the potential. During electrochemical evaluation, cathode
of MFC was used as counter electrode, Ag/AgCl (S) as reference
electrode and wastewater as electrolyte. Current and voltage were
monitored to evaluate polarization behavior at various external
resistances (50 X to 30 K X). Cell potential and anode potential
were measured against saturated Ag/AgCl (S) electrode. Outlet
from anode chamber of all MFC were monitored for COD, pH,
and VFA as per standard methods [34] to evaluate treatment
efciency.
3. Results and discussion
3.1. Performance of fuel cells with variable anodic surface
impregnations
3.1.1. Electrogenic activity
The experimental data clearly illustrated the positive function
of anodic surface coatings/modications with MWCNT and CNP
on electrogenic activity (Fig 1; Table 1). However, the performance
of fuel cell varied with type of anode used. During rst cycle of
operation MFCp showed maximum power density (PD) of

33

G. Mohanakrishna et al. / Applied Energy 95 (2012) 3137

MFCP

Power density (mW/m2)

250

MFCCNP
MFCMWCNT

200

150

100

50

0
0

96

192

288

384

480

Time (h)
Fig. 1. Performance of MFC with carbon nanopowder (MFCCNP) and carbon
nanotubes (MFCMWCNT) impregnated graphite anodes in comparison with plain
graphite electrode (MFCP) with respect to power density (PD) during ve cycles of
operation with DSW.

34.02 mW/m2. A gradual improvement in the power output was


observed with every additional feeding event which might be
due to the system adaptation tendency. Consistent improvement
in the power generation was registered up to fth cycle operation
(107.51 mW/m2). MFCCNP showed maximum PD of 109.09 mW/m2
during rst phase of operation which was comparatively on higher
side than plain graphite electrode (MFCP). Later, with every feeding
event, consistent improvement in power output was observed up
to third cycle operation (166.98 mW/m2) thereafter stabilized
(4th cycle-168.46 mW/m2; 5th cycle-165 mW/m2). MFCMWCNT
showed higher power output compared to both MFCCNP and MFCP.
Maximum PD of 148.8 mW/m2 was registered during rst cycle of
operation with MFCMWCNT. Similar to MFCCNP, consistent improvement in power density was observed up to third cycle of operation
(263.44 mW/m2) but with comparatively higher performance and
stabilized thereafter (4th cycle-267.77 mW/m2; 5th cycle267.14 mW/m2). Volumetric power production was also found to
be depend on the type of anodic impregnation used (MFCMWCNT,
3.69 mW/m3 > MFCCNP, 2.33 mW/m3 > MFCP, 1.49 mW/m3) (Table 1). The nanostructure impregnations on anode used in this
study showed positive inuence on the power output and also
facilitated in rapid stabilization of the fuel cell performance. This
might be attributed to the availability of higher surface area of anode. The power output showed direct correlation with the surface
area of impregnated material. This study also depicted the compatibility of nanomaterials with anaerobic consortia.

3.1.2. Response to variable external load


The polarization plots against potential and power density at
different resistances (100 X to 30 KX) visualizes current densities
in concurrence with the experimental variations (Fig. 2). Current
generation showed decreasing trend with increase in the resistance which is in concurrence with the fuel cell operation. At
30 KX resistance relatively less current output (<1 mA) was recorded in all three fuel cells. Rapid stabilization of voltage was observed at higher resistances (30 KX). However, relatively high
potential drop was observed at low resistances. Effective e- discharge observed at lower resistances might be the probable reason
for higher potential drop and slow stabilization of the voltage at
lower resistances. The point at which maximum power density
(PDMax) was observed on the polarization curve against voltage
and current density is marked as cell design point (voltage change
region) of that particular fuel cell. Effective performance with respect to power output can be obtained on the left side of the cell
design point. It is usual practice to operate the cell to the left side
of the power density peak and at a high voltage or low current density. MFCMWCNT exhibited highest power density of 31.37 mW/m2
with a cell design point of at 400 O followed by MFCCNP
(15.43 mW/m2; 300 O) and MFCP (9.23 mW/m2; 400 O). Relatively
higher power density was observed with surface modied anodes
compared to plain anode. Cell design point was observed relatively
at higher resistance for MFCMWCNT than MFCCNP evidencing better
performance of carbon nanotubes.
3.1.3. Bio-electrochemical behavior
Electrochemical behavior of fuel cells were evaluated in situ
employing cyclic voltammetry (CV). CV proles (vs Ag/AgCl (S) evidenced visible and signicant variation in electron (e ) discharge
pattern (Fig. 3). Among the three variations studied, MFCMWCNT
visualized maximum catalytic current in the forward sweep (FS,
17 mA) and reverse sweep (RS, 9.5 mA) followed by MFCCNP
[12.5 mA (FS) and
7.5 mA (RS)] and MFCP [5 mA (FS) and
3.75 mA (RS)] during stable phase of operation. The macroscale
porous structure of nano materials enlarges the anolyte-biolmanode interfacial area which improves the charge transfer from
the biocatalyst to the anode [28]. This might be the probable reason for the observed higher catalytic currents in both FS and RS
with nano material impregnated anodes. Redox signal pertaining
to the mediators were observed on the voltammograms drawn
with the three fuel cells studied. Oxidation peaks observed in the
voltammograms of three MFC were in the range of 0.25 V to
0.30 V, while reduction peaks were in the range of 0.09 V to
0.28 V. The oxidation and reduction signals evidence the involvement of cytochrome c during oxidation and avoproteins and/or
iron-sulfur proteins during reduction sweeps [35]. The intensity
of the redox peak was found to vary with the type of material
impregnated on anode and was found to be proportional to the

Table 1
Experimental output pertaining to the various anodic impregnations used in MFC operation with DSW and distillery wastewaters as substrates.

a
b

Output parameters

MFCPa

MFCCNPa

MFCMWCNTa

MFCDWb

OCV (max, mV)


Current at 50 X (max, mA)
Power at 50 X (mW)
Power density (mW/m2)
Sustainable resistance (KX)/ sustainable power density (mW/m2)
COD removal (mg/l)
Substrate degradation rate (SDR, kg CODR/m3-day)
Volumetric power yield (W/m3)
Specic power yield (SPY, W/kg CODR)
pH variation

242
3.11
0.75
107.52
11.0/4.41
2200
0.56
1.49
0.344
7.007.60

352
3.35
1.18
168.45
11.0/6.08
2350
0.57
2.33
0.537
6.957.35

426
4.40
1.87
267.77
11.0/11.25
2350
0.59
3.69
0.817
6.827.30

406
4.23
1.72
245.34
10.0/11.05
1800
0.45
3.43
0.954
7.007.60

Evaluated with DSW.


Evaluated with distillery based wastewater with MWCNT impregnated anode.

G. Mohanakrishna et al. / Applied Energy 95 (2012) 3137

a
30
-400
20

Anode potenatial (mV)

2
Voltage (mV) Power density (mW/m )

34

10
0
300

MFC P
MFC CNP
MFC MWCNT

200
100

-300

-200

MFCP

-100

MFCCNP
MFCMWCNT

0
0

100

200

300

400

500

600

Current density (mA/m )

10

15

20

25

30

Resistance ()

Fig. 2. Polarization behavior of three fuel cells during fth cycle of operation with
DSW.

b 100
MFCP

95

MFCCNP

20m

90

MFCMWCNT

85

MFCCNP

10m
5m

MFCP

RDAP (%)

Current (A)

15m

80
75

-5m

70

-10m

40

-15m
-0.75

MFCMWCNT

-0.50

-0.25

0.25

0.50

0.75

Voltage (V)
Fig. 3. Cyclic voltammetric (CV) proles of three MFC during fth cycle of operation
with DSW.

surface area of the anodic coating applied. The maximum redox


peaks were observed for MFCMWCNT followed by MFCCNP and MFCP.
Maximum power observed with MFCMWCNT and MFCCNP strongly
supports the higher bio-electrochemical activity and higher electron discharge.
3.1.4. Electron motive force
Variation in potentials of the anode, cathode and cell against the
external resistance were calculated during the stabilized phase of
operation. Cell emf (E0) decreased signicantly when the applied
resistance was less than 5 KX for all the fuel cells studied which
indicates the start up of reactor performance at 5 KX.Cathode potential (E0cathode) varied in a narrow range (85 4 mV) for all fuel
cells. Since, all fuel cells were operated with similar cathode, the
power generation was limited by the anode. E0anode controls the
kinetics of electron transfer from the biocatalyst to the anode.
Signicant drop in anode potential (E0anode) with external resistance was noticed during operation (Fig. 4a). E0anode suggested
the possibility of effective electron discharge below 10 KX of external resistance for all the anodes studied. Relative decrease in
anodic potential (RDAP) with the function of applied external resistance was used to evaluate the maximum sustainable power. The
linear t at high external resistance represents a region in which
the external resistance controls the power [36]. When external
resistance was high, the RDAP increased linearly with decreasing
external resistance because the electron delivery to the cathode

20
0
0

10

15

20

25

30

Resistance ()
Fig. 4. Fuel cell characterization with respect to (a) anode potential and (b) relative
decrease in anodic potential (RDAP).

was limited by external resistance. At applied low external resistance, the electron delivery to the cathode was limited by kinetic
and/or mass transfer, and the RDAP increased linearly with
decreasing external resistance. The conditions where external
and internal resistance limitations were equal between these two
lines, a horizontal line from the intersection were drawn to estimate the external resistor that allowed to measure sustainable
power (Fig. 4b). All fuel cell operations demonstrated similar sustainable resistance of 11 KX in concurrence with different sustainable power density. The maximum sustainable power density was
registered with MFCMWCNT (11.25 mW/m2) followed by MFCCNP
(6.08 mW/m2) and MFCP (4.41 mW/m2). Maximum sustainable
power density was observed with modied anodes indicating that
nanostructure impregnations provides more surface area which
gives more stability to the system at higher resistance.

3.1.5. Substrate degradation


The organic fraction of DSW functioned as an electron donor
during the metabolic process resulted in substrate degradation in
concurrence with the power generation. Substrate degradation
was found to increase consistently with increase in number of cycles operated (Fig. 5; Table 1). Consistent improvement in substrate degradation might be due to the adaptation of biocatalyst

35

G. Mohanakrishna et al. / Applied Energy 95 (2012) 3137

8.0
MFC P
MFC CNP
7.6

MFC MWCNT

pH

7.2

6.8

6.4

6.0
C1

C2

C3

C4

C5

formation of biolm at a faster rate [28]. Both MFCCNP and MFCP


showed almost similar substrate degradation. When specic power
yield (SPY) was evaluated, maximum value was observed with
MFCMWCNT (0.817 W/kg CODR) followed by MFCCNP (0.537 W/kg
CODR) and MFCP (0.344 W/kg CODR) (Fig. 5c, Table 1). Maximum
substrate degradation and specic power yield observed with
MFCMWCNT enumerated effective functioning or colonization of
mixed microora in MWCNT coated anode with possibility of
effective electron discharge. CNP impregnated anode also registered comparatively higher SPY than MFCP. Using carbon nanostructures also evidenced good biocompatibility with anaerobic
consortia. Redox conditions/pH of three fuel cells was found to
vary with in a narrow range (MFCP, 77.60; MFCCNP, 6.957.35;
MFCMWCNT, 6.827.30) during operation (Fig. 5c).
3.2. Performance of MWCNT impregnated anode using distillery
wastewater

Cycle number

b
1.5

1.0

0.5

0.0
MFCP

MFCCNP

MFCMWCNT

65

MFCP

COD removal efficiency (%)

MFCCNP
MFCMWCNT
60

55

250

50
C1

C2

C3

C4

C5

Cycle number
Fig. 5. Process evaluation of three MFC with respect to (a) pH variation (b) power
and specic power yield and (c) COD removal efciency during ve cycles of
operation with DSW.

Power density (mW/m2)

Power/Specific power yield

Power (mW)
power yield (W/kg CODR)

MFCMWCNT visualized effective power output with good bioelectrochemical function. Therefore, to study its practical applicability, real eld distillery wastewater (MFCDW) was used as anolyte
and evaluated its performance under similar operating conditions.
The experimental data documented good power output using distillery wastewater (Fig. 6; Table 1). During rst cycle of operation
PD of 127.27 mW/m2 was observed which gradually improved
with every additional feeding event as observed with DSW. Consistent improvement in the power output was registered up to fourth
cycle of operation where maximum PD of 245.35 mW/m2 was registered. Later in the fth cycle almost similar performance was registered (243.00 mW/m2). Compared to DSW operated MWCNTanode, the time required for stabilization was higher for MFCDW
which might be due to the complexity of the wastewater used as
anolyte. Even though the time required for stabilization was higher, the variation in power output was negligible. Volumetric power
yield of the MFCDW was registered as 3.43 W/m3 (Table 1).
During stabilization phase of operation, polarization curve
MFCDW evidenced 400 X as cell design point which is comparable
to the cell design point registered with MFCMWCNT (DSW)
(Fig. 7a). However, maximum power density observed with DW
(28.01 mW/m2) was comparatively lower than DSW. The stabilization of voltage at various resistances was also observed to be
similar in polarization with both the wastewaters. However, relatively higher potential drop was observed at low resistances when
operated with DW. E0cathode was found to be 84 5 mV which is

200

150

100

50

in the anodic chamber. Maximum COD removal was registered


with MFCMWCNT (COD removal efciency, 64.38%; substrate degradation rate (SDR), 0.59 kg CODR/m3-day) followed by MFCCNP
(61.91%, 0.57 kg CODR/m3-day) and MFCP (61.64%, 0.56 kg CODR/
m3-day). Carbon nanotube structure offers favorable environment
for the colonization of the mixed microora which helps in the

0
0

96

192

288

384

480

Time (h)
Fig. 6. Power generation potential of MFCDW with distillery wastewater as
substrate during ve cycles of operation.

G. Mohanakrishna et al. / Applied Energy 95 (2012) 3137

a
300

Voltage (V)

20
200

150
10
100

50

Voltage
Power density
0

100

200

Power density (mW/m2)

250

Current (A)

30

25m
20m
15m
10m
5m

Cycle 3

0
-5m
-10m
-15m
-20m
-25m
-0.75

Cycle 5
Cycle 1
-0.50

400

500

0.25

0.50

Fig. 8. Cyclic voltammograms (CV) of MFCDW.

600

Current density (mA/m )

50
7.6

Outlet pH
COD removal

80
45

60
40
7.4

20

pH

RDAP (%)

b 100

Anode potential (mV)

0.75

Voltage (V)

0
300

-0.25

0
400
300

40

7.2

35

200

COD removal efficicency (%)

36

100
0

7.0
0

10

15

20
Resistance (k )

25

30

Fig. 7. Fuel cell characterization of MFCDW (a) polarization study (b) anode
potential and RDAP during fth cycle of operation.

almost similar with the MFC operated with DSW. Signicant drop
in E0anode was noticed during operation of MFCDW (Fig. 7b). E0anode
suggested the possibility of effective electron discharge below
10 KX of external resistance similar to other experimental variations studied (Fig. 7b). E0 also decreased signicantly when resistance applied was less than 5 KX. The linear t drawn for RDAP
during the stabilized phase of MFCDW operation demonstrated to
possess the maximum sustainable power density of 11.05 mW/m2
and at sustainable resistance of 10.0 KX (Fig. 7b). Function of MFCDW
at higher resistance indicates the stability of the system in discharging the electrons effectively. The observation made from the cell
potentials and RDAP evidenced the application of the MWCNT
impregnated anode for improved performance of the fuel cells.
Bio-electrochemical behavior of MFCDW was evaluated during
ve cycles of operation. The catalytic current during FS
(23 0.5 mA) was almost similar throughout the ve cycles, while
the current during RS ( 15 6 mA) varied (Fig. 8). This is an evidence for strong oxidation along with reduction throughout the
ve cycles, which supports the increase in substrate utilization. Redox pairs were identied in CVs from third to fth cycles pertaining to the involvement of cytochrome c (0.25 V to 0.30 V) and
avoproteins or iron-sulfur proteins ( 0.09 V to 0.28 V) as mediators. The redox behavior of MWCNT impregnated anodes was almost similar with both DW and DSW. The catalytic currents were
less during rst cycle and found to increase with every additional
feeding event before stabilization from third cycle of operation.
Voltammograms of the third to fth cycles were very much similar
with negligible variation in the redox signals.

30
C1

C2

C3

C4

C5

Cycle number
Fig. 9. Evaluation of treatment of distillery wastewater using MFCDW with respect
to COD removal and pH variation.

The distillery wastewater showed feasibility of power generation along with wastewater treatment (Fig. 9). During ve cycles
of operation substrate degradation was found to increase consistently with the function of cycles due to the adaptation of consortia. First cycle operation showed lower substrate degradation
(45.20%) which gradually increased with number of cycles operated and registered maximum during fth cycle of operation
(49.32%, 0.45 kg CODR/m3-day). MFCDW showed SPY of 0.954 W/
kg CODR which is relatively on higher side compared to fuel cell
operation with DSW. Anolyte pH was found to vary between 7
and 7.6 during ve cycles of operation.
4. Conclusions
Nano structures impregnated anodes were employed to increase surface area of the graphite electrode using multiwalled carbon nanotubes (MWCNT) and carbon nanopowder (CNP) as surface
impregnations. Modied anodes depicted higher power output
than plain electrode which might be due to the effective colonization of microbial consortia. Modied electrodes also evidenced
improvement in wastewater treatment. Modied anodes also
found to show effective electron transfer by the involvement of
mediators such as avo proteins, iron-sulfur proteins and cytochrome c. Anode modied with MWCNT evidenced practical applicability in MFC operation with distillery wastewater. The
involvement of the mediators was also not effected with the usage
of real eld wastewater as substrate. In summary, the performance

G. Mohanakrishna et al. / Applied Energy 95 (2012) 3137

of the MFC was found to depend on the nature and surface area of
the anode.
Acknowledgements
Authors acknowledge the Director, CSIR-IICT for his support and
encouragement in carrying out this work. GM acknowledges the
Council for Scientic and Industrial Research (CSIR), New Delhi,
for providing senior research fellowship.
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